TWI822963B - Polymer materials and ophthalmic medical devices - Google Patents

Abstract

The present invention provides a silicone-containing polymer material that contains an internal wetting agent and has excellent transparency, and the antifouling property of the silicone-containing polymer material against lipids is improved. The polymer material of the present invention is a polymer material obtained by polymerizing a polymerizable mixture containing (a) a monomer component containing (a-1) and (b) a hydrophilic polymer component having silicon. A silicone-containing monomer having an oxyalkyl bond and not having a hydroxyl group, and (a-2) a compatibilizing monomer having a group having a hydrogen bonding proton and not having a silicon atom. The compatibilizing monomer has four or more carbon atoms (excluding the carbon atoms contained in the polymerizable functional group), and its solubility in water at 25° C. is less than 0.03 g/mL.

Description

Polymer materials and ophthalmic medical devices

The present invention relates to a polymer material, and more particularly to a polymer material suitable for use in ophthalmic lenses.

Contact lenses are roughly divided into hard contact lenses and soft contact lenses. In recent years, most hard contact lenses are made of silicone-containing polymers with a siloxane structure (Si-O-Si), which have high oxygen permeability. However, there are problems due to hardness. A foreign body sensation occurs when wearing the product. On the other hand, soft contact lenses are formed from a water-containing hydrogel (hydrogel) using a copolymer containing a hydrophilic monomer and a (meth)acrylic monomer as copolymer components, thereby achieving an excellent wearing feel. , on the other hand, tend to have lower oxygen permeability than hard contact lenses. In contrast, soft contact lenses using a silicone hydrogel containing a silicone monomer as a further copolymer component have been developed to achieve both high oxygen permeability and excellent wearing comfort.

However, soft contact lenses formed from silicone hydrogels are prone to lipids adhering to the surface. Therefore, lipid adhesion can be inhibited by plasma treatment or by mixing hydrophilic polymers as internal wetting agents in the hydrogel.

When an internal wetting agent is used, since the compatibility of the highly hydrophilic internal wetting agent with the highly hydrophobic silicone monomer is low, usually two or three are used to make the two compatible. Methylsilyloxy)silylpropylglycerolmethyl A silicone-containing monomer having a hydroxyl group such as methyl acrylate (also called "SiGMA") (for example, Patent Document 1). This makes it possible to obtain a transparent polymer material in which the adhesion of lipids is suppressed, but there is still a demand for further improvements in the antifouling properties of lipids.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2005-518826

The main object of the present invention is to provide a silicone-containing polymer material that contains an internal wetting agent and has excellent transparency, and the antifouling property of the polymer material against lipids is improved.

According to one aspect of the present invention, there is provided a polymer material obtained by polymerizing a polymerizable mixture including (a) a monomer component including (b) a hydrophilic polymer component. a-1) a silicone-containing monomer having a siloxane bond and not having a hydroxyl group and (a-2) a compatibilizing monomer having a group containing a hydrogen bonding proton and not having a silicon atom, the compatibilization The monomer has four or more carbon atoms (excluding the carbon atoms contained in the polymerizable functional group), and its solubility in water at 25° C. is less than 0.03 g/mL.

In one embodiment, the (a-2) compatibilizing monomer has six or more carbon atoms (excluding the carbon atoms contained in the polymerizable functional group).

In one embodiment, the (a) monomer component further includes (a-3) hydrophilic Single body.

In one embodiment, the proportion of the (b) hydrophilic polymer component in the polymerizable mixture is 1% by mass to the total compounding amount of the (a) monomer component and (b) the hydrophilic polymer component. 30% by mass.

In one embodiment, the (a-2) compatibilizing monomer has a polymerizable functional group, a middle part including a group containing hydrogen bonding protons, and a hydrophobic terminal part including two or more carbon atoms.

In one embodiment, the hydrophobic terminal portion includes a branched hydrocarbon group and/or a hydrocarbon group including a cyclic structure.

In one embodiment, the (a-2) compatibilizing monomer is represented by the following formula (A).

Z-A-B (A)

(In the formula, Z represents a (meth)acrylyl group, A contains a group containing hydrogen bonding protons, or represents a divalent atomic group that together with Z forms a group containing hydrogen bonding protons, and B represents a carbon number of 2 to 20 Hydrocarbon group, in which the total number of carbon atoms contained in A and B is 4 or more.)

In one embodiment, the divalent atomic group represented by A is represented by the following formula (i).

*-XR ^a1 -(L ^a1 ) _r1 -[(R ^a2 ) _r2 -(L ^a2 ) _r3 ] _r4 - (i)

⁽ In the formula, * represents ^a bond ^with Z ^, For an alkyl group of 1 to 4, L ^a1 and L ^a2 independently represent an ether bond, an ester bond, a carbonyl group, an amide bond, a urethane bond, or a urea bond, and r1 to r3 independently represent 0 or 1. r4 represents an integer from 0 to 10, where, when R ^a2 does not have a hydroxyl group, r3 and r4 are not 0, and the atomic group in (i) has at least one group containing a hydrogen bonding proton.)

In one embodiment, the R ^a1 represents an alkylene group having 1 to 6 carbon atoms having a hydroxyl group, r1 is 0 or 1, and r2 and r3 are 0.

In one embodiment, the hydrogen bonding proton-containing group includes a hydroxyl group.

In one embodiment, the silicone-containing monomer (a-1) contains nitrogen atoms.

In one embodiment, the weight average molecular weight of the (b) hydrophilic polymer component is 100,000 or more.

In one embodiment, the (b) hydrophilic polymer component is polyvinylamide.

In one embodiment, the (b) hydrophilic polymer component includes poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid and polyvinyl alcohol. At least one.

In one embodiment, the (b) hydrophilic polymer component is poly-N-vinylpyrrolidone.

In one embodiment, the Young modulus of the polymer material is 0.05MPa~2.0MPa.

According to another aspect of the present invention, an ophthalmic medical device is provided, which includes the polymer material.

In one embodiment, the ophthalmic medical device is a contact lens.

According to the present invention, a transparent silicone-containing polymer material containing an internal humectant is obtained, the antifouling properties of the polymer material against lipids being improved.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

The polymer material according to one embodiment of the present invention is obtained by polymerizing a polymerizable mixture containing (a) a monomer component and (b) a hydrophilic polymer component. More specifically, the monomer component (a) and the hydrophilic polymer component (b) are polymerized in a mixed state, preferably in a compatible state. The (b) hydrophilic polymer component used in the present invention is typically a non-polymerizable component that does not have a polymerizable functional group. In this state, the monomer component (a) is polymerized to obtain a product containing A polymer material in which a polymer derived from structural units of (a) a monomer component and (b) a hydrophilic polymer component are highly complexed.

In this specification, the term "monomer" refers to a polymerizable compound having one or more polymerizable functional groups. Therefore, polymerizable compounds composed of two or more monomer units (also called oligomers) and polymerizable compounds with large molecular weights (also called macromonomers or macromonomers) are also Contained in the monomer.

Examples of the polymerizable functional group include: (meth)acrylyl group, vinyl group, allyl group, and the like.

In this specification, "(methyl)" means any methyl substitution. Therefore, "(meth)acrylyl" means methacrylyl and/or acrylyl. The same applies to other descriptions such as "(meth)acrylic group".

A.Polymerizable mixture

The polymerizable mixture includes (a) a monomer component and (b) a hydrophilic polymer component, wherein the (a) monomer component includes (a-1) a silicone-containing polymer having a siloxane bond and not having a hydroxyl group. The monomer and the compatibilized monomer (a-2) have a group containing a hydrogen bonding proton and do not have a silicon atom. (a-2) Compatibilizing monomer compatibilizes (a-1) silicone-containing monomer and (b) hydrophilic polymer component, and can help improve antifouling against lipids properties, so polymer materials with excellent transparency and antifouling properties can be obtained. In addition, the polymerizable mixture may further contain any appropriate additive (c) if necessary.

In one embodiment, the polymerizable mixture does not substantially contain a silicone-containing monomer having a hydroxyl group, and more specifically, does not substantially contain a silicone-containing monomer having a hydroxyl group such as SiGMA. Here, "substantially does not contain a silicone-containing monomer having a hydroxyl group" means that the monomer in the polymerizable mixture is present relative to the total blending amount of (a) the monomer component and (b) the hydrophilic polymer component. The compounding ratio of the body is 0.1% by mass or less.

(a) Monomer components

The monomer component includes (a-1) a silicone-containing monomer having a siloxane bond and not having a hydroxyl group, and (a-2) a compatibilizing monomer having a group containing a hydrogen bond proton and not having a silicon atom. , preferably further containing (a-3) hydrophilic monomer. If necessary, the monomer component may further include one or more types selected from (a-4) crosslinking monomers, (a-5) functional monomers, and (a-6) other comonomers. The total content ratio of (a-1) silicone-containing monomer, (a-2) compatibilizing monomer, and (a-3) hydrophilic monomer in the entire monomer component can be set to, for example, 30% by mass~ 99% by mass, preferably 70% by mass to 95% by mass.

(a-1) Silicone-containing monomer

Since silicone-containing monomers have a siloxane structure (Si-O-Si), they can impart high oxygen permeability to polymer materials. As the silicone-containing monomer, any appropriate monomer can be used as long as it has a siloxane bond and does not have a hydroxyl group. In one embodiment, a silicone-containing monomer that does not have a hydroxyl group or an ionic group such as a carboxyl group, a sulfonic acid group, or a phosphate group can be used.

Examples of the silicone-containing monomer include those previously used as materials for contact lenses. Material monomers, such as silicone-containing monomers described in paragraphs 0039 to 0044 of Japanese Patent Publication No. 2015-503631 (excluding monomers having hydroxyl groups), Japanese Patent Publication No. 2014-40598 The silicone-containing monomer described in paragraphs 0060 to 0065 of WO2015/92858, the silicone-containing monomer described in paragraphs 0024 to 0037 of WO2015/92858 (specifically, the silicone-containing monomer is represented by the following formula (A), relatively Preferably, it is a polysiloxane macromonomer represented by formula (A-1), formula (A-2) or (A-3)). In this specification, these publications are incorporated by reference in their entirety. The silicone-containing monomer can be used alone or in mixture of two or more kinds.

[Chemical 1]A ¹ -Z ¹ -U ¹ -Z ² -Z ³ -(-S ¹ -U ² -) _n -S ² -Z ⁴ -Z ⁵ -U ³ -Z ⁶ -A ² ． ． ． (A)

In the general formula (A),

1)n is 0 or an integer from 1 to 10.

2) A ¹ and A ² are groups represented by the following general formula (A-II) and general formula (A-III), respectively. In the following general formula (A-II) and general formula (A-III), Y ²¹ and Y ²² are each independently an acryloxy group, a methacryloxy group, a vinyl group or an allyl group, and R ²¹ and R ²² are each independently a direct bond or a linear or branched alkylene group having 2 to 6 carbon atoms.

Y ²¹ -R ²¹ -. ． ． (A-II)

-R ²² -Y ²² ． ． ． (A-III)

3) Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ are each independently a polyoxyalkylene chain having a direct bond or an oxyalkylene group as a repeating unit. Among them, at least one of Z ¹ to Z ⁶ is a polyoxyethylene chain with a repeating number of oxyethylene groups of 2 or more, preferably 4 to 15, and not Z ¹ to Z ⁶ of a polyoxyethylene chain. At least one polyoxyalkylene chain having an oxyalkylene group different from the oxyethylene group as a repeating unit (for example, a polyoxypropylene chain having an oxypropylene group as a constituent unit). As a specific example, it is an oxyalkylene chain. A polyoxypropylene chain with a propyl repeat number of 5 to 16).

4) U ¹ is a group represented by the following general formula (A-IV), and the molecular chain of the polysiloxane-based macromonomer contains a urethane bond. In the following general formula (A-IV), E ²¹ is a -NHCO- group (in this case, E ²¹ and X ²¹ form a urethane bond), or is derived from a group selected from saturated or unsaturated aliphatic The divalent group of diisocyanate in the group consisting of series, alicyclic series and aromatic series (in this case, E ²¹ forms a urethane bond between Z ¹ and X ²¹ ), X ²¹ is an oxygen atom.

-E ²¹ -X ²¹ -． ． ． (A-IV)

5) U ² is a group represented by the following general formula (A-VI), and contains a urethane bond in the molecular chain of the polysiloxane-based macromonomer. In the following general formula (A-VI), R ⁴¹ and R ⁴² are each independently a linear or branched alkylene group having 2 to 6 carbon atoms, and X ⁴¹ and X ⁴² are each independently an oxygen atom or Alkanediol group, E ⁴¹ is a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic system, alicyclic system and aromatic system (in this case, E ⁴¹ is A urethane bond is formed between X ⁴¹ and X ⁴² ).

-R ⁴¹ -X ⁴¹ -E ⁴¹ -X ⁴² -R ⁴² -． ． ． (A-VI)

6) U ³ is a group represented by the following general formula (A-VII), and contains a urethane bond in the molecular chain of the polysiloxane-based macromonomer. In the following general formula (A-VII), X ²² is an oxygen atom, and E ²² is a -NHCO- group (in this case, E ²² forms a urethane bond with X ²² ), or A divalent group of diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic systems (in this case, E ²² forms between Z ⁵ and X ²² urethane bond).

-X ²² -E ²² -. ． ． (A-VII)

7) S ¹ and S ² are each independently a group represented by the following general formula (AV). In the following general formula (AV), R ³¹ and R ³⁸ are each independently a linear or branched alkylene group having 2 to 6 carbon atoms, and R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are each independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group. In addition, K is an integer from 1 to 1500, L is 0 or an integer from 1 to 1500, and the sum of K and L: "K+L" is an integer from 1 to 1500.

[Chemicalization 2]

(In the formula, R ⁵¹ represents a hydrogen atom or a methyl group, a is an integer of 2 or more, b is an integer of 2 or more, and n is an integer of 1 to 1500. In addition, R ⁵² and R ⁵³ are a hydrogen atom or a methyl group. , when R ⁵² is a hydrogen atom, R ⁵³ is a methyl group, and when R ⁵² is a methyl group, R ⁵³ is a hydrogen atom.)

[Chemical 4] General formula (A-2)

(In the formula, a' is an integer of 2 or more, b' is an integer of 2 or more, and n' is an integer of 1 to 1500. In addition, R ⁶¹ and R ⁶² are hydrogen atoms or methyl groups, and R ⁶¹ is hydrogen When R 62 is an atom, R ⁶² is a methyl group, and when R ⁶¹ is a methyl group, R ⁶² is a hydrogen atom.)

(In the formula, a" is an integer of 2 or more, b" is an integer of 2 or more, and n" is an integer of 1 to 1500. In addition, R ⁸¹ and R ⁸² are hydrogen atoms or methyl groups, and R ⁸¹ is hydrogen When R 82 is an atom, R ⁸² is a methyl group, and when R ⁸¹ is a methyl group, R ⁸² is a hydrogen atom.)

Other specific examples of the silicone-containing monomer include: (meth)acrylic acid trimethylsilyloxydimethylsilylmethyl ester, (meth)acrylic acid trimethylsilyloxydimethylsilylmethyl ester Propyl ester, (meth)acrylic acid methyl bis(trimethylsilyloxy)silylpropyl ester, (meth)acrylic acid tris(trimethylsilyloxy)silylpropyl ester, (meth)acrylic acid mono[ Methylbis(trimethylsilyloxy)silyloxy]bis(trimethylsilyloxy)silylpropyl ester, (meth)acrylic acid tris[methylbis(trimethylsilyloxy)silyloxy] ] Silylpropyl ester, (meth)acrylic acid methyl bis (trimethylsilyloxy) silyl propyl glyceryl ester, (meth) acrylic acid methyl bis (trimethylsilyloxy) silyl propyl glyceryl ester, (Meth)acrylic acid mono[methylbis(trimethylsilyloxy)silyloxy]bis(trimethylsilyloxy)silylpropylglyceride, (meth)acrylic acid trimethylsilylethyl Tetramethyldisiloxypropylglyceride, (meth)acrylic acid trimethylsilylmethyl ester, (meth)acrylic acid trimethylsilylpropylglyceride, (meth)acrylic acid trimethylsilylmethyl Propyl ester, (meth)acrylic acid trimethylsilyloxydimethylsilylpropylglyceride, (meth)acrylic acid methylbis(trimethylsilyloxy)silylethyltetramethyldisilanoxy methyl ester, (meth)acrylic acid tetramethyltriisopropylcyclotetrasiloxyalkylpropyl ester, (meth)acrylic acid tetramethyltriisopropylcyclotetrasiloxysilyloxybis(trimethylsilyloxy) )Silicone-containing (meth)acrylic alkyl esters such as silyl propyl ester; tris(trimethylsilyloxy)silylstyrene, bis(trimethylsilyloxy)methylsilylstyrene, ( Trimethylsilyloxy)dimethylsilylstyrene, tris(trimethylsilyloxy)silyloxydimethylsilylstyrene, [bis(trimethylsilyloxy)methylsilyloxy ]Dimethylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, heptamethyltrisiloxystyrene, nonamethyltetrasiloxystyrene, pentamethylsilylstyrene Heptasiloxyalkyl styrene, twenty-one Methyl decasiloxystyrene, heptadecamethyltridecasiloxystyrene, trimonomethylpentadecasiloxystyrene, trimethylsiloxypentamethyldisilaneoxy methylsilylstyrene, tris(pentamethylsilyloxy)silylstyrene, tris(trimethylsilyloxy)silyloxybis(trimethylsilyloxy)silylstyrene, bis(trimethylsilyloxy)silylstyrene (Heptamethyltrisiloxy)methylsilylstyrene, tris[methylbis(trimethylsilyloxy)silyloxy]silylstyrene, hepta(trimethylsilyloxy)trisilyl Styrene, trimethylsilyloxybis[tris(trimethylsilyloxy)silyloxy]silylstyrene, nonamethyltetrasilyloxyundecylmethylpentasiloxymethylsilyl Styrene, tris[tris(trimethylsilyloxy)silyloxy]silylstyrene, (tritrimethylsilyloxy)hexamethyltetrasilyloxy[tris(trimethylsilyloxy)silane Oxy]trimethylsilyloxysilylstyrene, nona(trimethylsilyloxy)tetrasilylstyrene, bis(tridedecamethylhexasilyloxy)methylsilylstyrene, heptamethyl Cyclotetrasiloxystyrene, heptamethylcyclotetrasiloxybis(trimethylsiloxy)silylstyrene, tripropyltetramethylcyclotetrasiloxystyrene, trimethylsilane Silicone-containing styrene derivatives such as styrene; bis(3-(trimethylsilyl)propyl)fumarate, bis(3-(pentamethyldisiloxy)propyl)fumarate Silicone-containing fumarate diesters such as malic acid ester and bis(tris(trimethylsilyloxy)silylpropyl)fumaric acid ester.

Further specific examples of the silicone-containing monomer include: mono(meth)acryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane, mono(meth)acryloxypropyl-terminated Oxypropyl-terminated mono-n-methyl-terminated polydimethylsiloxane, mono(meth)acryloxypropyl-terminated mono-n-butyl-terminated polydiethylsiloxane, mono(methyl) Acryloxypropyl-terminated mono-n-methyl-terminated polydiethylsiloxane, mono(meth)acrylyl Aminopropyl-terminated mono-n-butyl-terminated polydimethylsiloxane, mono(meth)acrylamidepropyl-terminated mono-n-methyl-terminated polydimethylsiloxane, mono(meth)acrylamidepropyl-terminated mono-n-methyl-terminated polydimethylsiloxane, (Methyl)acrylamidepropyl-terminated mono-n-butyl-terminated polydiethylsiloxane, mono(meth)acrylamidepropyl-terminated mono-n-methyl-terminated polydiethylsiloxane wait. In these silicone-containing monomers, the repeating number of (Si-O) can be, for example, 4 to 20, preferably 4 to 12, and more preferably 4 to 10.

In one embodiment, a silicone-containing monomer containing nitrogen atoms is used. Since the silicone-containing monomer contains nitrogen atoms, the compatibility with the hydrophilic monomer becomes higher. Through the synergistic effect with the compatibilizing monomer, even if the content of the silicone-containing monomer becomes It can also maintain the transparency of the lens.

The proportion of the silicone-containing monomer in the polymerizable mixture relative to the total compounding amount of (a) the monomer component and (b) the hydrophilic polymer component can be, for example, preferably 1 to 70 mass%. The content is 5 mass% to 60 mass%, more preferably 10 mass% to 50 mass%. If the blending ratio of the silicone-containing monomer is within this range, a polymer material with high oxygen permeability can be obtained.

(a-2) Compatibilizing monomer

Compatibilizing monomers can help improve the compatibility of hydrophilic polymer components with silicone-containing monomers and antifouling properties against lipids. As the compatibilizing monomer, a monomer that has a group containing a hydrogen bonding proton, does not have a silicon atom, and has four or more carbon atoms in addition to the carbon atoms contained in the polymerizable functional group can be used. In conventional silicone hydrogels containing a hydrophilic polymer (internal humectant), a hydroxyl group with high affinity for the hydrophilic polymer and a siloxane with high affinity for the silicone component were used. The silicone-containing monomer (typically SiGMA) in the (-Si-O-Si-) part ensures the compatibility between the silicone component and the hydrophilic polymer. On the other hand, in the present invention, even though a monomer without silicon atoms is used, better compatibility can be ensured compared to the case of using SiGMA, and the effect of improving the antifouling properties of lipids can also be obtained.

Examples of the hydrogen bond proton-containing group include a hydroxyl group, a carboxyl group, an amine group, an amide bond, a sulfonic acid group (-SO ₃ H), a urethane bond, and a urea bond. Among them, hydroxyl group is preferred. The number of hydrogen-bonding proton-containing groups of the compatibilizing monomer is, for example, 1 to 12, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

The number of carbon atoms (excluding carbon atoms contained in the polymerizable functional group) of the compatibilizing monomer is, for example, 6 or more, preferably 6 to 25, more preferably 7 to 15, and even more preferably 8 to 13. In the compatibilizing monomer, for example, each group containing hydrogen bonding protons has more than four carbon atoms, and may have more preferably 5 to 15 carbon atoms, and even more preferably 8 to 13 carbon atoms.

The solubility of the compatibilizing monomer in water at 25° C. is typically less than 0.03 g/mL, preferably 0.02 g/mL or less, and more preferably 0 g/mL to 0.01 g/mL. By using a monomer that has a hydrogen-bonding proton-containing group such as a hydroxyl group but is hydrophobic as a whole, it can help improve the relationship between the silicone-containing monomer and the hydrophilic polymer or hydrophilic monomer. compatibility.

In one embodiment, the compatibilizing monomer not only has a polymerizable functional group and a group containing hydrogen bonding protons, but also has a hydrophobic group containing two or more carbon atoms, preferably four or more carbon atoms. In this embodiment, it is preferable that the compatibilizing monomer has a polymerizable functional group, a middle portion including a group containing a hydrogen bonding proton, and two More specifically, it is preferable that a polymerizable functional group is arranged on one of the terminal parts of the compatibilized monomer molecule, a hydrophobic group is arranged on the other terminal part, and the hydrophobic terminal part of more than one carbon atom is preferably arranged. A relatively highly hydrophilic group containing a group containing hydrogen bonding protons is arranged between them. A compatibilizing monomer that has a group containing a hydrogen bonding proton at a position relatively close to a polymerizable functional group such as a (meth)acrylyl group and a terminal hydrophobic group at a relatively distant position can improve hydrophilic properties. Both the polymer and the silicone-containing monomer exhibit excellent affinity.

The compatibilizing monomer of the embodiment can be represented by the following formula (A).

Z-A-B (A)

(In the formula, Z represents a (meth)acrylyl group, A contains a group containing hydrogen bonding protons, or represents a divalent atomic group that together with Z forms a group containing hydrogen bonding protons, and B represents a carbon number of 2 to 20 Hydrocarbon group, in which the total number of carbon atoms contained in A and B is 4 or more.)

In the formula (A), the divalent atomic group specified in A can be represented by the following formula, for example: *-XR ^a1 -(L ^a1 ) _r1 -[(R ^a2 ) _r2 -(L ^a2 ) _r3 ] _r4 - ( i)

⁽ Here ^, * represents a ^{bond with} Z, For an alkyl group of 1 to 4, L ^a1 and L ^a2 independently represent an ether bond, an ester bond, a carbonyl group, an amide bond, a urethane bond, or a urea bond, and r1 to r3 independently represent 0 or 1. r4 represents an integer from 0 to 10, where, when R ^a2 does not have a hydroxyl group, r3 and r4 are not 0, and the atomic group in (i) has at least one group containing a hydrogen bonding proton.)

R ^a1 and R ^a2 each independently preferably represent an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, and more preferably represent an alkylene group having 1 to 4 carbon atoms which may have a hydroxyl group. Specifically, it is preferable that at least one of R ^a1 and R ^a2 has a hydroxyl group, and it is more preferable that R ^a1 has a hydroxyl group. Examples of such an embodiment include an embodiment in which R ^a1 has a hydroxyl group and R ^a2 does not exist (for example, an embodiment in which r1 = 0 or 1, r2 = 0, and r3 = 0), or an embodiment in which both R ^a1 and R ^a2 have Embodiments of hydroxyl groups (for example, embodiments in which r1=1, r2=1, r3=0 or 1), etc.

When L ^a1 and L ^a2 are present, L ^a1 and L ^a2 may each independently preferably be an ether bond or an ester bond. Among them, when both R ^a1 and R ^a2 do not have a hydroxyl group, it is preferable that at least one of L ^a1 and L ^a2 be a amide bond, a urethane bond, or a urea bond.

The hydrocarbon group specified in B may be linear or branched, may include a cyclic structure, or may include heteroatoms at any position. The hetero atom is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogens such as fluorine. B can be preferably an unsubstituted or fluorine-substituted hydrocarbon group (for example, an alkyl group) having 4 to 20 carbon atoms, and more preferably 5 to 12 carbon atoms.

Specific examples of the compatibilizing monomer according to the embodiment are shown in the following formula (I), formula (V) or formula (VI).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represent an alkylene group having 1 to 6 carbon atoms, and R ⁴ represents a hydrocarbon group having 2 to 20 carbon atoms. From -(R ^5a ) _s -OR ^5b , -(R ^5a ) _s -O(C=O)-R ^5b or -(R ^5a ) _s The structure represented by -(C=O)OR ^5b (here, R ^5a represents carbon number 1~ 4 alkylene group, R ^5b represents a hydrocarbon group with 2 to 20 carbon atoms, s represents 0 or 1), X ¹ represents O or NR ⁶ , (here, R ⁶ represents hydrogen or an alkyl group with 1 to 4 carbon atoms) , X ² represents a single bond or ^an alkylene group with ₁ ^{to 3} _carbon atoms, -(R ^7a ) _t -O(C=O)-(R ^7b ) _u -, -(R ^7a ) _t -(C=O)O-(R ^7b ) _u -, -(R ^7a ) _t -( C=O)-(R ^7b ) _u -or the structure represented by the following formula (II) ~ formula (IV),

(Here, R ^7a represents an alkylene group having 1 to 4 carbon atoms, R ^7b represents an alkylene group having 1 to 20 carbon atoms, and R ^8a and R ^8b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , t and u independently represent 0 or 1), n is an integer from 0 to 10, q1 and q2 independently represent 0 or 1, where, after removing the polymerizable functional group (CH ₂ =CR ¹ -CO-) The total number of carbon atoms contained in the residues is 3 or more, and the hydrocarbon group or alkyl group specified in R ⁴ , R ^5b , R ⁶ , R ^8a and R ^8b may each independently have a heteroatom. )

Regarding formula (I), the hydrocarbon group specified in R ⁴ and R ^5b is preferably an aliphatic hydrocarbon group having 2 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 4 to 10 carbon atoms (for example, alkyl). These hydrocarbon groups may be linear or branched, or may include a cyclic structure. It is thought that these hydrocarbon groups function as terminal hydrophobic groups, thereby allowing the compatibilizing monomer to exhibit affinity for the silicone-containing monomer.

Specific examples of the hydrocarbon group specified for R ⁴ or R ^5b include: ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl linear alkyl groups such as isopropyl, methylpropyl, tert-butyl, dimethylpropyl, ethylpropyl, diethylpropyl, methylbutyl, dimethylbutyl, trimethylpropyl Methylbutyl, ethylbutyl, propylbutyl, methylpentyl, dimethylpentyl, ethylpentyl, propylpentyl, butylpentyl, methylhexyl, dimethylhexyl, Trimethylhexyl, ethylhexyl, propylhexyl, butylhexyl, methylheptyl, dimethylheptyl, ethylheptyl, propylheptyl, methyloctyl, dimethyloctyl, ethyl Branched alkyl groups such as octyl and methylnonyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclononyl; cyclooctylethyl , cycloheptylmethyl, cycloheptylethyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl , cyclopentylpentyl, cyclobutylpropyl, cyclobutylbutyl, cyclobutylpentyl, cyclopropylbutyl, cyclopropylpentyl, cyclopropylhexyl and other alkyl groups containing cycloalkyl rings ; Norbornyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, butyladamantyl and other bridged cyclic alicyclic hydrocarbon groups.

The groups of R ⁶ , R ^8a and R ^8b are each preferably hydrogen or an alkyl group having 1 or 2 carbon atoms.

^{The alkylene groups specified in} Ethyl.

The alkylene group specified in R ^7b is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms.

The total number of carbon atoms contained in the groups of X ² and R ² is preferably 3 or less, more preferably 0 to 2, and ^even more preferably 1 or 2 (for example, There are embodiments in which R ² is used (that is, an embodiment in which q1=0); embodiments in which both X ² and R ² are methylene groups, etc.). It is thought that the compatibilizing monomer can exhibit affinity for the hydrophilic polymer by arranging the hydroxyl group close to the (meth)acrylyl group.

The total number of carbon atoms contained in the group of X ³ is preferably 0 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

The hetero atom that the hydrocarbon group or alkyl group specified for R ⁴ , R ^5b , R ⁶ , R ^8a and R ^8b may have is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogens such as fluorine and the like. In one embodiment, the hydrocarbon group or alkyl group specified in R ⁴ , R ^5a , R ⁶ , R ^8a or R ^8b may be a fluoroalkyl group or a perfluoroalkyl group.

Preferably n is 0~5, more preferably 0, 1 or 2.

In one embodiment, in formula (I), R ¹ is a hydrogen atom or a methyl group, X ¹ is O, X ² is methylene or ethylidene, preferably methylene, n is 0, and R ⁴ is -(R ^5a ) _s -OR ^5b (where R ^5a is methylene, s is 1, R ^5b is a hydrocarbon group with 2 to 20 carbon atoms that can be substituted by fluorine), q1 is 0 or 1, preferably 0 .

In one embodiment, in formula (I), R ¹ is a hydrogen atom or a methyl group, X ¹ is O, X ² is methylene or ethylidene, preferably methylene, n is 0, and R ⁴ is -(R ^5a ) _s -O(C=O)-R ^5b (where R ^5a is methylene, s is 1, R ^5b is a hydrocarbon group with 2 to 20 carbon atoms that can be substituted by fluorine), q1 is 0 Or 1, preferably 0.

In one embodiment, in formula (I), R ¹ is a hydrogen atom or a methyl group, X ¹ is O, X ² is methylene or ethylidene, preferably methylene, n is 0, and R ⁴ is For a hydrocarbon group having 2 to 20 carbon atoms which may be substituted by fluorine, q1 is 0 or 1, preferably 0.

(In the formula, R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a hydrocarbon group with 4 to 20 carbon atoms, represented by -OR ^10b or -R ^10a -OR ^10b , -R ^10a -O(C=O)-R ^10b , -R ^10a -(C=O)OR ^10b or -R ^10a -(C=O)-R ^10b (Here, R ^10a represents an alkylene group having 1 to 4 carbon atoms, and R ^10b represents an alkylene group having 2 to 20 carbon atoms. A structure represented by a hydrocarbon group), wherein the total number of carbon atoms contained in the group of R ¹⁰ is 4 or more, and the hydrocarbon group specified in R ¹⁰ or R ^10b may have a heteroatom.)

Regarding the formula (V), the hydrocarbon group specified in R ¹⁰ or R ^10b is preferably an aliphatic hydrocarbon group having 4 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group (for example, an alkyl group) having 4 to 10 carbon atoms. These hydrocarbon groups may be linear or branched, or may include a cyclic structure. It is thought that these hydrocarbon groups function as terminal hydrophobic groups, thereby allowing the compatibilizing monomer to exhibit affinity for the silicone-containing monomer.

Specific examples of the hydrocarbon group specified for R ¹⁰ or R ^10b include the same hydrocarbon groups as specific examples of the hydrocarbon group specified for R ⁴ or R ^5b (among them, hydrocarbon groups having four or more carbon atoms).

The alkylene group specified in R ^10a is preferably methylene, ethylene, propylene or butylene, more preferably methylene or ethylene.

The hetero atom that the hydrocarbon group specified in R ¹⁰ or R ^10b may have is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogens such as fluorine and the like. In one embodiment, the hydrocarbon group specified in R ¹⁰ or R ^10b may be a fluoroalkyl group or a perfluoroalkyl group.

⁽ In the formula, R ¹¹ represents ^a hydrogen ^atom or a ^methyl group, Alkyl group, X ⁵ is a single bond, O or a structure represented by the following formulas (VII) to formula (IX),

(Here, R ^15a and R ^15b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and R ¹³ represents a hydrocarbon group having 2 to 20 carbon atoms. When X ⁴ is not NH, X ⁵ is In a structure containing a urethane bond (-NHCOO-) or a urea bond (-NHCONH-), R ¹² , R ¹³ , R ¹⁴ , R ^15a and R ^15b may each independently have a heteroatom. )

Regarding formula (VI), the alkylene group specified in R ¹² may be linear or branched, or may include a cyclic structure. R ¹² is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an ethylene group, a propylene group, or a butylene group.

The hydrocarbon group specified in R ¹³ is preferably an aliphatic hydrocarbon group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 4 to 10 carbon atoms (for example, an alkyl group). The hydrocarbon group may be linear or branched, or may include a cyclic structure. It is thought that the hydrocarbon group functions as a terminal hydrophobic group, so that the compatibilizing monomer can exhibit affinity for the silicone-containing monomer.

Specific examples of the hydrocarbon group specified for R ¹³ include the same hydrocarbon groups as specific examples of the hydrocarbon group specified for R ⁴ or R ^5b .

Specific examples of the alkyl group specified for R ¹⁴ , R ^15a and R ^15b include a methyl group or an ethyl group.

The hetero atoms that R ¹² , R ¹³ , R ¹⁴ , R ^15a and R ^15b may have are not limited as long as the effects of the present invention can be obtained, and examples thereof include halogens such as fluorine. In one embodiment, R ¹² , R ¹³ , R ¹⁴ , R ^15a or R ^15b may be a fluoroalkyl group or a perfluoroalkyl group.

In another embodiment, the compatibilizing monomer includes a (meth)acrylyl group, four or more carbon atoms, and an alicyclic ring having at least one hydrogen atom substituted with a group containing hydrogen bonding protons. Examples of the alicyclic ring include preferably an alicyclic ring having 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 8 to 12 carbon atoms, and may be an alicyclic ring having a bridged structure. As a specific example of the compatibilizing monomer in this embodiment, a preferred example is one having a More specifically, (meth)acrylates of more than one hydroxyl-substituted bridged cycloalicyclic group (for example, adamantyl, norbornyl, tricyclodecyl, tetracyclododecyl, etc.) Preferred examples include hydroxy(meth)acryloxyadamantane, dihydroxy(meth)acryloxyadamantane, and the like.

The proportion of the compatibilizing monomer in the polymerizable mixture can be, for example, 1 to 60 mass % relative to the total compounding amount of (a) the monomer component and (b) the hydrophilic polymer component, and is preferably 1 to 60 mass %. 5 mass% to 50 mass%, more preferably 10 mass% to 40 mass%. If the blending ratio of the compatibilizing monomers is within this range, a polymer material that maintains high oxygen permeability and has excellent transparency and antifouling properties can be obtained.

(a-3) Hydrophilic monomer

The hydrophilic monomer imparts hydrophilicity to the silicone-containing polymer produced by the polymerization of the monomer component (a), thereby making it possible to form a polymer that is a composite of the polymer and the hydrophilic polymer component (b). Material made into hydrogel. As the hydrophilic monomer, for example, a monomer with a solubility in water of 25° C. of 0.03 g/mL or more can be used (except for monomers containing silicon atoms and monomers having two or more polymerizable functional groups). .

Specific examples of the hydrophilic monomer include hydroxyl-containing (meth)acrylic alkyl groups such as (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, (meth)acrylic acid dihydroxypropyl ester, etc. Esters; N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N-isopropyl( (Meth)acrylamide, N-acrylylmorpholine and other (meth)acrylamide; N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam and other N- Vinyl lactam; 1-methyl-3-methylene-2-pyrrolidinone and other N-methyl lactams. Among them, (methyl) can be preferably used 2-hydroxyethyl acrylate, N,N-dimethyl(meth)acrylamide, N-acrylylmorpholine and 1-methyl-3-methylene-2-pyrrolidinone. The hydrophilic monomer can be used alone or in mixture of two or more types.

The blending ratio of the hydrophilic monomer in the polymerizable mixture can be, for example, 0.1 mass % to 90 mass %, preferably 20 mass %, relative to the total blending amount of (a) the monomer component and (b) the hydrophilic polymer component. Mass % to 80 mass %, more preferably 25 mass % to 70 mass %, further preferably 25 mass % to 50 mass %. If the blending ratio of the hydrophilic monomer is within this range, a polymer material with high moisture content and surface hydrophilicity can be obtained.

(a-4) Cross-linkable monomer

The crosslinkable monomer is added as necessary for the purpose of improving the mechanical strength or shape stability of the polymer material. As the crosslinkable monomer, a monomer having two or more polymerizable functional groups can be used.

Specific examples of the crosslinkable monomer include butylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and di(meth)acrylate. Triethylene glycol acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, allyl fumarate, allyl (meth)acrylate, vinyl (meth)acrylate Ester, trimethylolpropane tri(meth)acrylate, methacryloyloxyethyl (meth)acrylate, divinylbenzene, diallyl phthalate, diallyl adipate , triallyl diisocyanate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth)acrylate, 3-vinylbenzyl (meth)acrylate, 2,2- Bis((meth)acryloxyphenyl)hexafluoropropane, 2,2-bis((meth)acryloxyphenyl)propane alkane, 1,4-bis(2-(meth)acryloxyhexafluoroisopropyl)benzene, 1,3-bis(2-(meth)acryloxyhexafluoroisopropyl)benzene, 1,2-bis(2-(meth)acryloxyhexafluoroisopropyl)benzene, 1,4-bis(2-(meth)acryloxyisopropyl)benzene, 1,3- Bis(2-(meth)acryloxyisopropyl)benzene, 1,2-bis(2-(meth)acryloxyisopropyl)benzene, etc. Among them, butylene glycol di(meth)acrylate and/or ethylene glycol di(meth)acrylate can be preferably used. The crosslinkable monomer can be used alone or in mixture of two or more types.

The proportion of the crosslinkable monomer in the polymerizable mixture may be, for example, 0% to 3% by mass relative to the total amount of the (a) monomer component and (b) the hydrophilic polymer component, preferably 0% to 3% by mass. 0.1 mass% to 2.5 mass%, more preferably 0.3 mass% to 2 mass%, further preferably 1.0 mass% to 1.8 mass%. If the blending ratio of the crosslinkable monomer is within this range, a polymer material with good mechanical strength can be obtained.

(a-5) Functional monomer

Functional monomers are added as necessary for the purpose of imparting predetermined functions to polymer materials. Examples of functional monomers include polymerizable dyes, polymerizable ultraviolet absorbers, polymerizable ultraviolet absorbing dyes, and the like.

Specific examples of the polymerizable dye include: 1-phenylazo-4-(meth)acryloxynaphthalene, 1-phenylazo-2-hydroxy-3-(meth)acryloxynaphthalene Oxynaphthalene, 1-naphthylazo-2-hydroxy-3-(meth)acrylyloxynaphthalene, 1-(α-anthracenylazo)-2-hydroxy-3-(meth)acrylamide Oxynaphthalene, 1-((4'-(phenylazo)-phenyl)azo)-2-hydroxy-3-(meth)acryloxynaphthalene, 1-(2',4'- Dimethylphenylazo)-2-(meth)acryloxynaphthalene, 1-(o-tolylazo)-2-(meth)acryloxynaphthalene, 2-(m-(meth)propene Amido-anilino)-4,6-bis(1'-(o-tolylazo)-2'-naphthylamino)-1,3,5-triazine, 2-(m-vinylanilino) )-4-((4'-nitrophenylazo)-anilino)-6-chloro-1,3,5-triazine, 2-(1'-(o-tolylazo)-2' -Naphthyloxy)-4-(m-vinylanilino)-6-chloro-1,3,5-triazine, 2-(p-vinylanilino)-4-(1'-(o-tolyl) Nitrogen)-2'-naphthylamino)-6-chloro-1,3,5-triazine, N-(1'-(o-tolylazo)-2'-naphthyl)-3-vinyl Phthalic acid monoamide, N-(1'-(o-tolylazo)-2'-naphthyl)-6-vinyl phthalic acid monoamide, 3-vinyl phthalic acid- (4'-(p-Sulfophenylazo)-1'-naphthyl) monoester, 6-vinyl phthalic acid-(4'-(p-Sulfophenylazo)-1'-naphthyl) hydroxy) monoester, 3-(meth)acrylamide-4-phenylazophenol, 3-(meth)acrylamide-4-(8'-hydroxy-3',6'-disulfo -1'-naphthylazo)-phenol, 3-(meth)acrylamide-4-(1'-phenylazo-2'-naphthylazo)-phenol, 3-(methyl) Acrylamide-4-(p-tolylazo)phenol, 2-amino-4-(m-(2'-hydroxy-1'-naphthylazo)anilino)-6-isopropenyl-1, 3,5-Triazine, 2-amino-4-(N-methyl-p-(2'-hydroxy-1'-naphthylazo)anilino)-6-isopropenyl-1,3,5 -Triazine, 2-amino-4-(m-(4'-hydroxy-1'-phenylazo)anilino)-6-isopropenyl-1,3,5-triazine, 2-amino -4-(N-methyl-p-(4'-hydroxyphenylazo)anilino)-6-isopropenyl-1,3,5-triazine, 2-amino-4-(m-( 3'-methyl-1'-phenyl-5'-hydroxy-4'-pyrazolylazo)anilino)-6-isopropenyl-1,3,5-triazine, 2-amino- 4-(N-methyl-p-(3'-methyl-1'-phenyl-5'-hydroxy-4'-pyrazolylazo)anilino)-6-isopropenyl-1,3, 5-Triazine, 2-amino-4-(p-phenylazoanilino)-6-isopropenyl-1,3,5-triazine, 4-phenylazo-7-(methyl) Azo polymeric dyes such as acrylamide-1-naphthol; 1,5-bis((meth)acrylamide)-9,10-anthraquinone, 1-(4'-vinylbenzyl) amide)-9,10-anthraquinone, 4-amino-1-(4'-vinylbenzamide)-9,10-anthraquinone, 5-amino -1-(4'-vinylbenzamide)-9,10-anthraquinone, 8-amino-1-(4'-vinylbenzamide)-9,10-anthraquinone, 4- Nitro-1-(4'-vinylbenzamide)-9,10-anthraquinone, 4-hydroxy-1-(4'-vinylbenzamide)-9,10-anthraquinone, 1 -(3'-vinylbenzamide)-9,10-anthraquinone, 1-(2'-vinylbenzamide)-9,10-anthraquinone, 1-(4'-isopropenyl Benzamide)-9,10-anthraquinone, 1-(3'-isopropenylbenzamide)-9,10-anthraquinone, 1-(2'-isopropenylbenzamide)- 9,10-anthraquinone, 1,4-bis(4'-vinylbenzamide)-9,10-anthraquinone, 1,4-bis(4'-isopropenylbenzamide)-9 ,10-anthraquinone, 1,5'-bis(4'-vinylbenzamide)-9,10-anthraquinone, 1,5-bis(4'-isopropenylbenzamide)-9 ,10-anthraquinone, 1-methylamino-4-(3'-vinylbenzamide)-9,10-anthraquinone, 1-methylamino-4-(4'-vinylbenzene Methyloxyethylamino)-9,10-anthraquinone, 1-amino-4-(3'-vinylphenylamino)-9,10-anthraquinone-2-sulfonic acid, 1- Amino-4-(4'-vinylphenylamino)-9,10-anthraquinone-2-sulfonic acid, 1-amino-4-(2'-vinylbenzylamino)-9, 10-Anthraquinone-2-sulfonic acid, 1-amino-4-(3'-(meth)acryloylaminophenylamino)-9,10-anthraquinone-2-sulfonic acid, 1- Amino-4-(3'-(meth)acrylamidebenzylamino)-9,10-anthraquinone-2-sulfonic acid, 1-(β-ethoxycarbonylallylamino) )-9,10-anthraquinone, 1-(β-carboxyallylamino)-9,10-anthraquinone, 1,5-di-(β-carboxyallylamino)-9,10- Anthraquinone, 1-(β-isopropoxycarbonylallylamino)-5-benzamide-9,10-anthraquinone, 2-(3'-(meth)acrylamide-anilino) )-4-(3'-(3"-sulfo-4"-aminoanthraquinone-1"-yl)-amino-anilino)-6-chloro-1,3,5-triazine, 2 -(3'-(meth)acrylamide-anilino)-4-(3'-(3"-sulfo-4"-aminoanthraquinone-1"-yl)-amino-anilino) -6-hydrazino-1,3,5-triazine, 2,4-bis-((4"-methoxyanthraquinone-1"-yl)-amino)-6-(3'-vinyl Anilino)-1,3,5-triazine, 2-(2'-vinylphenoxy)-4-(4'-(3"-sulfo-4"-aminoanthraquinone-1"- (Amino)-anilino)-6-chloro-1,3,5-tri Azine, 1,4-bis(4-(2-methacryloxyethyl)phenylamino)9,10-anthraquinone, 1,4-bis((2-methacryloxyethyl) Anthraquinone-based polymeric dyes such as 9,10-anthraquinone; nitro-based polymeric dyes such as o-nitroanilinomethyl (meth)acrylate; (meth)acrylamide copper tetramine Phthalocyanine-based polymeric dyes such as phthalocyanine and (meth)acrylated (dodecyl tetraaminocopper phthalocyanine) are used. These can be used individually or in mixture of 2 or more types.

Specific examples of the polymerizable ultraviolet absorber include 2-hydroxy-4-(meth)acryloxybenzophenone and 2-hydroxy-4-(meth)acryloxy-5- 3-Butylbenzophenone, 2-hydroxy-4-(meth)acryloxy-2',4'-dichlorobenzophenone, 2-hydroxy-4-(2'-hydroxy-3 Benzophenone-based polymerizable ultraviolet absorbers such as '-(meth)acryloxypropoxy)benzophenone; 2-(2'-hydroxy-5'-(meth)acryloxyethane ylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth)acryloxypropylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-(meth)acryloxypropyl) Base-3'-tert-butylphenyl)-5-chloro-2H-benzotriazole, 2-(2'-hydroxy-5'-(2"-methacryloxyethoxy)- 3'-tert-butylphenyl)-5-methyl-2H-benzotriazole and other benzotriazole polymerizable ultraviolet absorbers; 2-hydroxy-4-methacrylyloxymethylbenzoic acid Salicylic acid derivatives such as phenyl ester are polymerizable UV absorbers; 2-cyano-3-phenyl-3-(3'-(meth)acryloxyphenyl)acrylic acid methyl ester, etc. These can Use alone or in combination of two or more.

Specific examples of the polymerizable ultraviolet absorbing dye include: 2,4-dihydroxy-3(p-styrene azo)benzophenone, 2,4-dihydroxy-5-(p-styrene azo)benzophenone, 2,4-dihydroxy-3-((meth)acryloyloxymethylphenylazo)benzophenone, 2,4-dihydroxy-5-((meth)acryloyloxymethylphenylazo)benzophenone p-(meth)acryloxymethylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-(meth)acryloxyethylphenylazo)benzophenone Ketone, 2,4-dihydroxy-5-(p-(meth)acryloxyethylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-(meth)acrylyl Oxypropylphenylazo)benzophenone, 2,4-dihydroxy-5-(p-(meth)acryloyloxypropylphenylazo)benzophenone, 2,4-di Hydroxy-3-(o-(meth)acryloxymethylphenylazo)benzophenone, 2,4-dihydroxy-5-(o-(meth)acryloxymethylphenylazo) Nitrogen) benzophenone, 2,4-dihydroxy-3-(o-(meth)acryloyloxyethylphenylazo)benzophenone, 2,4-dihydroxy-5-(o-(meth)acryloyloxyethylphenylazo)benzophenone, Methylacryloxyethylphenylazo)benzophenone, 2,4-dihydroxy-3-(o-(meth)acryloxypropylphenylazo)benzophenone, 2,4-Dihydroxy-5-(o-(meth)acryloxypropylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-(N,N-bis(methyl) hydroxy)acryloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-5-(p-(N,N-di(methyl)acryloxyethylamino) )phenylazo)benzophenone, 2,4-dihydroxy-3-(o-(N,N-di(meth)acryloyloxyethylamino)phenylazo)benzophenone , 2,4-dihydroxy-5-(o-(N,N-di(meth)acrylylethylamine)phenylazo)benzophenone, 2,4-dihydroxy-3-( p-(N-ethyl-N-(meth)acryloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-5-(p-(N-ethyl-N -(meth)acryloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-3-(o-(N-ethyl-N-(meth)acryloxy) Ethylamine)phenylazo)benzophenone, 2,4-dihydroxy-5-(o-(N-ethyl-N-(meth)acryloyloxyethylamino)phenyl Azo)benzophenone, 2,4-dihydroxy-3-(p-(N-ethyl-N-(meth)acrylamide)phenylazo)benzophenone, 2,4 -two Hydroxy-5-(p-(N-ethyl-N-(meth)acrylamide)phenylazo)benzophenone, 2,4-dihydroxy-3-(o-(N-ethyl) -N-(meth)acrylamide)phenylazo)benzophenone, 2,4-dihydroxy-5-(o-(N-ethyl-N-(meth)acrylamide) benzophenone-based polymeric UV-absorbing pigments such as hydroxy)phenylazo)benzophenone; or benzoic acid-based polymeric UV-absorbing pigments such as 2-hydroxy-4-(p-styrylazo)phenyl benzoate Pigments, etc. These can be used individually or in mixture of 2 or more types.

Relative to the total compounding amount of (a) the monomer component and (b) the hydrophilic polymer component, the total compounding amount of the functional monomer can be, for example, 0.001 mass % to 5 mass %, preferably 0.05 mass %. ~3% by mass.

(a-6) Other comonomers

As other copolymerizable monomers other than the above-mentioned (a-1) to (a-5), any appropriate monomer can be selected depending on the purpose. For example, from the viewpoint of improving copolymerization reactivity and adjusting the hardness or mechanical strength of the polymer material, alkyl (meth)acrylate having an alkyl group with a carbon number of 1 to 20, preferably 1 to 5, can be used. ; Alkoxyalkyl (meth)acrylate, etc., the carbon number of the alkoxyalkyl group is 1 to 20, preferably 1 to 5.

The proportion of other copolymerized monomers in the polymerizable mixture can be, for example, 0 mass % to 40 mass %, preferably 0, relative to the total compounding amount of (a) the monomer component and (b) the hydrophilic polymer component. mass%~30 mass%, more preferably 0 mass%~20 mass%.

(b) Hydrophilic polymer component

As the hydrophilic polymer component, any appropriate polymer capable of imparting surface hydrophilicity to the polymer material can be used. For example, polyvinylamide (e.g., Polymers such as poly(vinyllactam), polyamide, polylactone, polyimide, and polylactam are used as hydrophilic polymers. Among them, polymers whose main chain or side chain contains a cyclic structure, such as a cyclic amide structure or a cyclic amide imine structure, can be preferably used. The hydrophilic polymer may also be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer containing two or more monomers. In addition, as the hydrophilic polymer component, only one type of hydrophilic polymer may be used, or two or more hydrophilic polymers may be used in combination.

Specific examples of the hydrophilic polymer include poly-N-vinylpyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly -N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2- Piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone and poly-N-vinyl-4, 5-Dimethyl-2-pyrrolidinone, polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol, poly(meth)acrylic acid, poly(2-hydroxyethyl)(methyl) ) acrylates, polyalkylene glycols such as polyethylene glycol, poly-2-ethyl-oxazoline, heparin-polysaccharides, polysaccharides, and copolymers of these. Among them, poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid, polyvinyl alcohol, poly(2-hydroxyethyl)(meth)acrylate, etc. can be preferably used. .

The weight average molecular weight of the hydrophilic polymer may be, for example, 100,000 or more, preferably 150,000 to 2,000,000, more preferably 300,000 to 1,800,000, even more preferably 500,000 to 1,500,000.

The K value of the hydrophilic polymer can be, for example, 30~150, preferably 60~ 120, preferably 90~120. Here, the K value can be measured by Method 1 of Viscometry <2.53> in the 16th revised Japanese Pharmacopoeia. According to the method recorded in the "K value" column of the Pharmacopoeia, Fickenscher ( Fikentscher) formula and find it.

The compounding amount of the (b) hydrophilic polymer component in the polymerizable mixture can be typically set to 1 mass % with respect to 100 parts by mass of the total compounding amount of the (a) monomer component and (b) the hydrophilic polymer component. ~30 mass%, preferably 3 mass% to 25 mass%, more preferably 5 mass% to 20 mass%. If the compounding amount of the hydrophilic polymer component is within this range, a polymer material with high water content and excellent surface hydrophilicity can be obtained.

(c)Additives

As the additive, any appropriate additive can be selected depending on the purpose. Examples of additives include polymerization initiators, organic solvents, and the like.

The polymerization initiator can be appropriately selected according to the polymerization method. Examples of the thermal polymerization initiator used in polymerization by heating include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentane) Nitrile), benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, lauryl peroxide, tert-butyl peroxycaproate, 3,5,5- Trimethylhexyl peroxide, etc. These thermal polymerization initiators may be used alone or in combination of two or more.

The blending amount of the thermal polymerization initiator in the polymerizable mixture is preferably 0.001 to 2 parts by mass relative to 100 parts by mass of the total blending amount of (a) the monomer component and (b) the hydrophilic polymer component. Preferably, it is 0.01 to 1 part by mass.

As a photopolymerization starter used in polymerization by light irradiation Agents, for example, include: 2,4,6-trimethylbenzoyldiphenyl phosphine oxide (TPO), bis(2,4,6-trimethyl Phosphine oxide photopolymerization initiators such as benzoyl)-phenylphosphine oxide; methyl o-benzoyl benzoate, methyl benzoate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin isobutyl ether, benzoin n-butyl ether and other benzoin photopolymerization initiators; 2-hydroxy-2-methyl-1-phenylpropan-1-one (2-hydroxy-2-methyl-1-phenylpropan-1-one) -1-one, HMPPO), p-isopropyl-α-hydroxyisobutylphenone, p-tert-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetophenone, N,N-tetraethyl-4,4-diaminobenzophenone and other benzophenone photopolymerization initiators; 1-hydroxycyclohexyl Phenyl ketone; 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) oxime; 2-chlorothioxanthone, 2-methylthioxanthone and other thioxanthone series photopolymerized Starting agent; dibenzocycloheptanone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; benzil, etc. These photopolymerization initiators can be used alone or in combination of two or more. In addition, a photosensitizer may be used together with the photopolymerization initiator.

The preferred amount of the photopolymerization initiator and photosensitizer in the polymerizable mixture is 0.001 parts by mass~ relative to 100 parts by mass of the total amount of the (a) monomer component and (b) the hydrophilic polymer component. 2 parts by mass, preferably 0.01 to 1 part by mass.

The organic solvent may be a water-soluble organic solvent with high polarity, or a water-insoluble organic solvent with low polarity. As the water-soluble organic solvent, alcohols with 1 to 4 carbon atoms, acetone, methyl ethyl ketone, dimethyl formamide, dimethyl styrene, acetonitrile, N-methyl-2-pyrrolidone, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, etc. By using a water-soluble organic solvent, the compatibility between monomer components or between a hydrophilic polymer component and a monomer component can be improved. In addition, water-soluble organic solvents can be easily removed from polymeric materials by immersion in water.

As the water-insoluble organic solvent, hexane, cyclohexane, heptane, octane, dimethyl ether, diethyl ether, benzene, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, dichloro Methane, chloroform, carbon tetrachloride, alcohols with more than 6 carbon atoms, etc. By using a water-insoluble organic solvent, the compatibility between monomer components or between a hydrophilic polymer component and a monomer component can be improved. In addition, when added to a polymerizable mixture, the dynamic viscosity of the polymerizable mixture is reduced compared with the case of using a water-soluble organic solvent, so it can be easily handled.

The compounding amount of the organic solvent in the polymerizable mixture may be, for example, 50 parts by mass or less, preferably 40 parts by mass or less, based on 100 parts by mass of the total compounding amount of (a) the monomer component and (b) the hydrophilic polymer component. , more preferably 30 parts by mass or less. In the present invention, since the compatibility of each component in the polymerizable mixture is good, there is no need to prepare an organic solvent, or the amount of the organic solvent can be reduced.

As additives other than the above, additives previously used for ophthalmic lens applications may be used. Examples include cooling agents, thickeners, surfactants, non-polymerizable pigments, ultraviolet absorbers or ultraviolet absorbing pigments.

The amount of the other additives in the polymerizable mixture may be, for example, 0.01 to 5 parts by mass relative to 100 parts by mass of the total amount of the (a) monomer component and (b) the hydrophilic polymer component. The best is 0.01 parts by mass to 3 parts by mass share.

B. Polymerization method

The polymer material of the present invention can be obtained, for example, by heating and/or irradiating light (ultraviolet and/or visible light) to a polymerizable mixture containing each of the above components, so that each unit in the polymerizable mixture Body composition copolymerization. In addition, it can also be obtained by copolymerization using electron beam irradiation instead of light irradiation.

As the polymerization method, a block polymerization method or a solution polymerization method can be used. In the block polymerization method, a part of the monomer component may remain in an unpolymerized state. In addition, in the solution polymerization method, a solvent that does not participate in the reaction may remain in the polymer obtained. In the manufacture of contact lenses as medical devices, in order to minimize these residues, the following treatment can be carried out: by immersing the obtained polymer material in water or an organic solvent or a mixed solution thereof, preferably This operation is repeated to precipitate these residues and remove them from the polymer material.

When the polymer material of the present invention is used as a material for ophthalmic lenses such as contact lenses, the polymerizable mixture can be reacted by a molding method. When the polymerizable mixture is heated and polymerized by the molding method, the polymerizable mixture is filled into a mold corresponding to the shape of the desired ophthalmic lens material, and the mold is slowly processed. Heat.

The heating temperature and heating time when heating the polymerizable mixture in the mold are appropriately set depending on the composition of the polymerizable mixture and the like. The heating temperature is preferably from 50°C to 150°C, more preferably from 60°C to 140°C. In addition, the heating time when heating the polymerizable mixture in the mold is preferably 10 minutes or more. And less than 120 minutes, more preferably more than 20 minutes and less than 60 minutes.

In the molding method, when the polymerizable mixture is polymerized by light irradiation, the polymerizable mixture is filled into a mold corresponding to the shape of a desired ophthalmic lens material, and then the mold is irradiated with light. The material of the mold used for polymerization by light irradiation is not particularly limited as long as it can transmit light required for polymerization.

The wavelength of the light irradiated to the polymerizable mixture in the mold is appropriately set depending on the type of photopolymerization initiator used and the like. The illumination intensity and irradiation time are appropriately set according to the composition of the polymerizable mixture and the like. The ideal illumination intensity is 0.1mW/cm ² ~100mW/cm ² or less. The irradiation time is preferably more than 1 minute. Light with different illuminances can also be illuminated in stages.

By polymerization using the casting method, a polymer material having a desired shape can be obtained. The obtained polymer material as a molded body may also be subjected to mechanical processing such as cutting processing and grinding processing if necessary. Cutting may be performed throughout one or both surfaces of the polymer material, or may be performed on a portion of one or both surfaces of the polymer material.

Since the polymer material of the present invention contains a hydrophilic polymer component as an internal wetting agent, it has excellent surface hydrophilicity. However, for the purpose of further surface modification, low-temperature plasma treatment, atmospheric pressure plasma, and corona discharge can be implemented Surface modification treatment etc.

C. Characteristics of polymer materials

The oxygen permeability coefficient (Dk value) of the polymer material according to one embodiment of the present invention is relatively Preferably it is 20 Barrer or more, more preferably 30 Barrer or more, and even more preferably 50 Barrer~150 Barrer.

The moisture content of the polymer material according to one embodiment of the present invention is preferably 11 mass% or more, more preferably 30 mass% or more, and further preferably 30 mass% to 70 mass%. By setting the moisture content of the polymer material to 11% by mass or more, the obtained polymer material can be made into a hydrogel, which can improve the wearing feel when processed into contact lenses, and can set the strength, transparency and balance in a balanced manner. Oxygen and surface wettability.

The Young's modulus of the polymer material according to one embodiment of the present invention is preferably 0.05MPa to 2.0MPa, more preferably 0.1MPa to 1.5MPa, and even more preferably 0.3MPa to 1.5MPa. By setting the Young's modulus of the polymer material to 0.05MPa to 2.0MPa, both the wearing feel and operability when processed into contact lenses can be achieved.

[Example]

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited by these examples. In addition, unless otherwise stated, "parts" and "%" in Examples and Comparative Examples are based on mass.

[Ingredients used]

The meanings of the abbreviations of the components used in the following Examples and Comparative Examples are shown below.

(1) Hydrophilic polymer

． PVP (K-90, K-120): polyvinylpyrrolidone

(2)Silicone-containing monomers

． AA-PDMS: polymerizable silicone compound having the structure shown below

． Silicone macromonomer A: In the general formula (A-2), a'=6, b'=10, n=39

． TRIS: tris(trimethylsiloxy)silylpropylmethacrylate (structure shown below)

(3) Compatibilized monomer

． EH(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 25°C: less than 0.01g/mL)

[Chemical 13]

． tBu(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 25°C: less than 0.01g/mL)

． HADA: A polymeric compound having the structure shown below (manufactured by Mitsubishi Gas Chemical Co., Ltd.) (solubility in water at 25°C: less than 0.01 g/mL)

． DHADM: A polymeric compound having the structure shown below (Mitsubishi Gas Manufactured by a chemical company) (solubility in water at 25°C: less than 0.01g/mL)

． MA(OH)OCO(OH)Hp: A polymerizable compound having the following structure (solubility in water at 25°C: less than 0.01g/mL)

． C ₄ F ₉ CH ₂ CH(OH)CHMA: A polymerizable compound having the structure shown below (solubility in water at 25°C: less than 0.01 g/mL)

[Chemical 18]

． tBuCO(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 25°C: less than 0.01g/mL)

． CyCO(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 25°C: less than 0.01g/mL)

． AdaCO(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 25°C: less than 0.01g/mL)

． iPr(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 25°C: less than 0.01g/mL)

(4) Silicone-containing monomer with hydroxyl group

． SiGMA: (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsilyloxy)methylsilane (structure shown below)

(5)Hydrophilic monomer

． DMAA: N,N-dimethylacrylamide

． HEMA: 2-hydroxyethyl methacrylate

(6) Cross-linking monomer

． BDDA: 1,4-butanediol diacrylate

(7) Functional monomer

． HMEPBT: benzotriazole-based polymerizable ultraviolet absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole)

(8)Additives

． TPO: initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide)

． IPA: isopropyl alcohol

[Synthesis Example 1: Preparation of EH(OH)MA]

1) Add ethylhexyl glycidyl ether, methacrylic acid, tetrabutylammonium bromide, and p-methoxyphenol to a brown eggplant-shaped flask and dissolve them. Install a Daisch condenser and place in an oil bath at 90°C. Stir overnight.

2) Return the reaction solution to room temperature, dissolve it in hexane, and transfer it to a separatory funnel.

3) Wash the hexane layer with 1M sodium bicarbonate aqueous solution.

4) Use distilled water to clean the hexane layer.

5) Wash the hexane layer with saturated brine.

6) Recover the hexane layer, add an appropriate amount of sodium sulfate, dry it, and leave it for a period of time.

7) Remove sodium sulfate by filtering.

8) Concentrate the hexane layer under reduced pressure to obtain a slightly yellow transparent liquid. The hydrogen spectrum nuclear magnetic resonance ( ¹ H NMR) (CDCl ₃ , 400 MHz) and the gas chromatograph (gas chromatograph) were measured to confirm that the desired ^compound was obtained.

[Synthesis Example 2: Preparation of tBu(OH)MA]

Synthesis and purification were performed in the same manner as in Synthesis Example 1, except that ethylhexyl glycidyl ether was replaced with tert-butyl glycidyl ether.

[Synthesis Example 3: Preparation of MA(OH)OCO(OH)Hp]

1) Add 2-hydroxyoctanoic acid, glycidyl methacrylate, 4-dimethylaminopyridine, and p-methoxyphenol to a brown eggplant-shaped flask, install a Daisch condenser, and place in an oil bath at 85°C. Stir overnight.

2) Return the reaction solution to room temperature, dissolve it in ethyl acetate, and transfer it to a separatory funnel.

3) Wash the ethyl acetate layer with saturated sodium chloride aqueous solution.

4) Wash the ethyl acetate layer with a solution of saturated sodium bicarbonate aqueous solution: distilled water = 5:1.

5) Wash the ethyl acetate layer with distilled water.

6) Wash the ethyl acetate layer with saturated brine.

7) Recover the ethyl acetate layer, add an appropriate amount of sodium sulfate, dry it, and leave it for a period of time.

8) Remove sodium sulfate by filtering.

9) Concentrate the ethyl acetate layer under reduced pressure to obtain a transparent liquid. ¹ H NMR (CDCl ₃ , 400 MHz) and gas chromatography were measured to confirm that the desired compound was obtained.

[Synthesis Example 4: Preparation of C ₄ F ₉ CH ₂ CH(OH)CHMA]

Replace ethylhexyl glycidyl ether with 2,2,3,3,4,4,5,5,5-nonafluoropentylethylene oxide, replace tetrabutylammonium bromide with triethylamine, except Except for this, synthesis and purification were carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 5: Preparation of tBuCO(OH)MA]

Synthesis was performed in the same manner as in Synthesis Example 1, except that ethylhexyl glycidyl ether was replaced with glycidyl methacrylate, methacrylic acid was replaced with trimethylacetic acid, and the reaction temperature was set to 60°C. , purification.

[Synthesis Example 6: Preparation of CyCO(OH)MA]

The same procedure as Synthesis Example 1 was performed except that ethylhexyl glycidyl ether was replaced with glycidyl methacrylate, methacrylic acid was replaced with cyclohexanecarboxylic acid, and the reaction temperature was 60°C. Synthesis and purification.

[Synthesis Example 7: Preparation of AdaCO(OH)MA]

Synthesis and purification were performed in the same manner as in Synthesis Example 1, except that ethylhexyl glycidyl ether was replaced with glycidyl methacrylate and methacrylic acid was replaced with 1-adamantanecarboxylic acid.

[Synthesis Example 8: Preparation of iPr(OH)MA]

Synthesis and purification were performed in the same manner as in Synthesis Example 1, except that ethylhexyl glycidyl ether was replaced with glycidyl isopropyl ether.

[Example 1]

7 parts by mass of PVP (K-90) (manufactured by BASF) as a hydrophilic polymer, 28 parts by mass of AA-PDMS as a silicone-containing monomer, and EH(OH) as a compatibilizing monomer )MA 28 parts by mass, 30 parts by mass of DMAA and 7 parts by mass of HEMA as hydrophilic monomers, 1.4 parts by mass of BDDA as a cross-linkable monomer, 1.8 parts by mass of HMEPBT as a polymerizable ultraviolet absorber, and 0.4 parts by mass of TPO as the starting agent was mixed to prepare a polymerizable mixture without using a solvent. The polymerizable mixture was poured into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens with a diameter of 14.2 mm and a thickness of 0.08 mm). Then, the casting mold was irradiated with light emitting diode (LED) light at room temperature to perform photopolymerization. After polymerization, the contact lens-shaped polymer material is removed from the mold. With this, get contact lenses.

[Example 2 to Example 13 and Comparative Example 1 to Comparative Example 8]

A contact lens was obtained in the same manner as in Example 1, except that each component was mixed so as to have the composition described in Table 1 or 2 to prepare a polymerizable mixture.

The contact lenses obtained in the Examples and Comparative Examples were immersed in distilled water to swell until equilibrium was reached, and then replaced with a pH 7.5 phosphate buffer solution and allowed to swell until equilibrium was reached. Thereafter, the phosphate buffer solution was replaced with the same amount of new phosphate buffer solution, and the solution was autoclaved at 121° C. for 20 minutes, and then the following characteristic evaluation was performed. However, in the measurement of the oxygen permeability coefficient, a plate-shaped sample was used instead of a contact lens-shaped sample using a PP mold that can obtain a plate-shaped sample with an average thickness of about 0.3 mm. Casting mold, otherwise the same as above It is polymerized, hydrated and sterilized, and processed into a round shape with a diameter of 14.0mm. The results are shown in Table 1 to Table 2.

<<Appearance evaluation>>

Observe the appearance of the contact lens with the naked eye.

<<Evaluation of lipid adhesion>>

1) Place 1 g of solid artificial lipid (product name "Pharmasol") into each well of a multi-well plate at room temperature, and heat to melt at 80°C.

2) Wipe off the moisture on the surface of the contact lens, put the contact lens into each hole, place it at room temperature for one night, and then place it at 60°C for 1 hour.

3) Take out the contact lens from the hole, wash it in the contact lens cleaning solution (manufactured by Menicon, product name "Epicacold") put in the beaker, and use the contact lens cleaning solution (Manufactured by Menicon, product name "Epicacold") Scrub 30 times.

4) Place contact lens cleaning solution (manufactured by Menicon, product name "Epicacold") and contact lenses into each well of the multi-well plate, and leave them at 10°C overnight.

5) Take out the contact lens from the hole, confirm the appearance with the naked eye, and evaluate based on the following criteria.

[Judgment criteria]

0: Almost no whitening is observed

1: Only part of the whitening is observed

2: Approximately 50% of the entire body was observed to turn white.

3: It is observed that the lens is generally white as a whole, but there are parts with light turbidity in various places.

4: The entire lens is observed to turn white.

<<Moisture content determination>>

The water on the surface of the contact lens adjusted in a pH 7.5 phosphate buffer at 20° C. was gently wiped off, and the mass (W (g)) in the equilibrium water-containing state was measured. Thereafter, the lens was dried using a desiccator set to 105° C., and then the mass (W ₀ (g)) of the lens while left to cool was measured. Using the measured values W ₀ and W, the moisture content (mass %) was calculated according to the following formula.

Moisture content (mass %)={(WW ₀ )/W}×100

<<Measurement of tensile elastic modulus (Young’s modulus)>>

The produced contact lens was punched, and a dumbbell-shaped sample with a stretched portion width of about 1.8 mm and a thickness of about 0.1 mm was produced as a test sample. A tensile test was performed in physiological saline at 20°C using a Shimadzu precision universal testing machine Autograph AG-IS MS manufactured by Shimadzu Corporation, and the Young's modulus (MPa) was calculated from the stress-tensile curve as Tensile modulus of elasticity. Set the stretching speed to 100mm/min.

<<Measurement of oxygen permeability coefficient (Dk value)>>

As described above, a circular plate-shaped sample with a diameter of 14.0 mm was used as a measurement sample. As a reference standard (reference standard), use the "Two Weeks Menikon Pre The same plate sample was made from the raw materials of "2WEEK Menicon Premio" (manufactured by Menicon Company), and its Dk value was set to 129.

The measurement sample was placed on the electrode, and nitrogen gas was bubbled in physiological saline at 35° C. using a Seiko type thin film oxygen permeability meter (manufactured by Rika Seiki Industry Co., Ltd.), and the current value when the equilibrium state was reached was set to zero. Then, oxygen was bubbled, and the current value when the equilibrium state was reached was recorded. Do the same for reference standards. Calculate the oxygen transmission coefficient of the lens based on the following formula. Furthermore, the unit of oxygen permeability coefficient is (×10 ^-11 (cm ² /sec). (mLO ₂ /(mL×mmHg)) = Barrer).

Dk value=R×(IS/IR)×(TS/TR)×(PR/PS)

Here, the symbols in the formula have the following meanings.

R: Dk value of reference standard (129)

IS: Measure the current value of the sample (μA)

IR: reference standard current value (μA)

TS: Measure the average thickness of the sample (mm)

TR: average thickness of reference standard (mm)

PS: Atmospheric pressure (mmHg) when measuring the sample

PR: Atmospheric pressure (mmHg) when measured with reference standard

As shown in Table 1, the contact lenses of the Examples have high transparency and show superior antifouling properties against lipids compared with the contact lenses of the Comparative Examples. In addition, as shown in Table 2, it was found that the contact lenses of the Examples have practically sufficient oxygen permeability and moisture content, and have mechanical strength suitable for contact lens applications.

[Example 14~Example 17]

A contact lens was obtained in the same manner as in Example 1, except that each component was mixed so as to have the composition described in Table 3 to prepare a polymerizable mixture.

The contact lenses obtained in Examples 14 to 17 were immersed in distilled water and allowed to swell until equilibrium was reached, and then replaced with a pH 7.5 phosphate buffer solution and allowed to swell until equilibrium was reached. Thereafter, the phosphate buffer solution was replaced with the same amount of new phosphate buffer solution and sterilized in an autoclave at 121° C. for 20 minutes, and then subjected to the same appearance evaluation and lipid adhesion evaluation as in Example 1. The results are shown in Table 3.

As shown in Table 3, the contact lenses of the Examples can achieve practically sufficient transparency and have excellent antifouling properties against lipids.

[Example 18 and Example 19]

A contact lens was obtained in the same manner as in Example 1, except that each component was mixed so as to have the composition described in Table 4 to prepare a polymerizable mixture.

The contact lenses obtained in Examples 18 and 19 were immersed in distilled water and allowed to swell until equilibrium was reached, and then replaced with a pH 7.5 phosphate buffer solution and allowed to swell until equilibrium was reached. Thereafter, the phosphate buffer solution was replaced with the same amount of new phosphate buffer solution and sterilized in an autoclave at 121° C. for 20 minutes. The solution was subjected to the same appearance evaluation and lipid adhesion evaluation as in Example 1, and each characteristic was measured. Show the results in in Table 4.

As shown in Table 4, the contact lenses of the Examples had high transparency and showed excellent antifouling properties against lipids. In addition, it was found that the contact lenses of the Examples have practically sufficient oxygen permeability and moisture content, and have mechanical strength suitable for contact lens applications.

[Industrial availability]

The polymer material of the present invention is preferably used in ophthalmic medical devices, such as contact lenses, intraocular lenses, artificial corneas, cornea onlays, cornea inlays and other ophthalmic lenses.

Claims (18)

A polymer material obtained by polymerizing a polymerizable mixture containing (a) a monomer component containing (a-1) having a siloxane bond and (b) a hydrophilic polymer component. A silicone-containing monomer that does not have a hydroxyl group and (a-2) a compatibilization monomer that has a group containing a hydrogen bonding proton and does not have a silicon atom, and the compatibilization monomer has four or more carbon atoms (excluding carbon atoms contained in the polymerizable functional group), and the solubility in water at 25°C is less than 0.03g/mL, relative to the (a) monomer component and the (b) hydrophilic polymerization The total blending amount of the material components, the blending ratio of the compatibilizing monomer is 5 mass% to 50 mass%. The polymer material according to claim 1, wherein the (a-2) compatibilizing monomer has more than six carbon atoms (excluding the carbon atoms contained in the polymerizable functional group). The polymer material according to claim 1 or claim 2, wherein the (a) monomer component further includes (a-3) hydrophilic monomer. The polymer material according to claim 3, wherein the (b) in the polymerizable mixture is The blending ratio of the hydrophilic polymer component is 1 mass% to 30 mass%. The polymer material according to claim 1, wherein the (a-2) compatibilizing monomer has a polymerizable functional group, a middle part containing a group containing hydrogen bonding protons, and a hydrophobic terminal portion containing two or more carbon atoms. The polymer material of claim 5, wherein the hydrophobic terminal portion includes a branched hydrocarbon group and/or a hydrocarbon group including a cyclic structure. The polymer material according to claim 1, wherein the (a-2) compatibilizing monomer is represented by the following formula (A), Z-A-B (A) (in the formula, Z represents (meth)acrylamide Group, A includes a group containing hydrogen bonding protons, or a divalent atomic group that together with Z forms a group containing hydrogen bonding protons, B represents a hydrocarbon group with 2 to 20 carbon atoms, where the carbons contained in A and B The total number is 4 or more). The polymer material according to claim 7, wherein the divalent atomic group represented by A is represented by the following formula (i), *-XR ^a1 -(L ^a1 ) _r1 -[(R ^a2 ) _r2 - (L ^a2 ) _r3 ] _r4 - (i)(In the formula, * represents the bond with Z, X represents O or NR ^a3 , R ^a1 and R ^a2 each independently represent a carbon number of 1 to 20 that may have a hydroxyl group Alkylene group, R ^a3 represents hydrogen or an alkyl group with 1 to 4 carbon atoms, L ^a1 and L ^a2 independently represent an ether bond, an ester bond, a carbonyl group, an amide bond, a urethane bond, or a urea bond, r1~r3 independently represent 0 or 1, r4 represents an integer from 0 to 10, where, when R ^a2 does not have a hydroxyl group, r3 and r4 are not 0, and the atomic group in (i) has at least one hydrogen bonding property. sub-basis). The polymer material according to claim 8, wherein R ^a1 represents an alkylene group having hydroxyl groups having 1 to 6 carbon atoms, r1 is 0 or 1, and r2 and r3 are 0. The polymer material of claim 1, wherein the hydrogen bonding proton-containing group includes a hydroxyl group. The polymer material of claim 1, wherein the (a-1) silicone-containing monomer contains nitrogen atoms. The polymer material according to claim 1, wherein the (b) hydrophilic polymer component has a weight average molecular weight of 100,000 or more. The polymer material according to claim 1, wherein the (b) hydrophilic polymer component is polyvinylamide. The polymer material according to claim 1, wherein the (b) hydrophilic polymer component comprises poly-N-vinylpyrrolidone, polyalkylene glycol, polyalkylene glycol, At least one of sugar, poly(meth)acrylic acid and polyvinyl alcohol. The polymer material according to claim 1, wherein the (b) hydrophilic polymer component is poly-N-vinylpyrrolidone. The polymer material as described in claim 1, wherein the Young's modulus is 0.05MPa~2.0MPa. An ophthalmic medical device, comprising the polymer material described in any one of claim 1 to claim 16. The ophthalmic medical device as described in claim 17, which is a contact lens.